Upon a pressure vessel reactor, lower alkanes such as methane and propane subjected to temperatures of up to 800 k and pressures up to 70,000 psi (467 MPa), isomerize even in the absence of catalyst to produce a variety of alkanes, alkenes, cycloalkanes and aromatic hydrocarbons containing up to twelve carbon atoms.
|
15. A process for preparing higher hydrocarbons from a feedstock consisting essentially of c1 14 Cphd 3 alkanes which comprises reacting at least one Cphd 114 Cphd 3 alkane in the absence of catalyst at temperature from about 725K to about 825K at a pressure from about 50,000 (333 MPa) to 65,000 psi (433 MPa).
13. A process for converting a feedstock consisting essentially of one or more hydrocarbons to higher product hydrocarbons having up to 12 carbon atoms which comprises heating one or more c1 14 c3 alkane hydrocarbons at a temperature from about 625K to about 775K at a pressure from about 40,000 psi (267 MPa) to about 70,000 psi (467 MPa).
1. A process for converting a feedstock consisting essentially of one or more c1 -c3 hydrocarbons to product hydrocarbons having up to 12 carbon atoms which comprises heating in the absence of catalyst one or more c1 -c3 alkane hydrocarbons at a temperature from about 625 k to about 775 k at a pressure from about 40,000 psi (267 MPa) to about 70,000 psi (467 MPa).
9. A process for converting propane to higher molecular weight hydrocarbons said process comprising heating propane in the absence of a catalyst at a temperature of about 750 k at a pressure of about 60,000 psi (400 MPa) for a time sufficient to produce one or more hydrocarbons having up to 12 carbon atoms selected from the group consisitng of branched or straight chain alkanes, branched or straight chain unsaturated aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons.
12. A process for synthesizing higher hydrocarbons products by adding c1 or c2 hydrocarbon units to saturated hydrcarbons selected from the group consisting of c1 -c3 alkanes which comprise the steps of:
1) combining in the absence of catalyst c1 14 c3 alkane hydrocarbon with gaseous methane in a volume ratio of from 5:95 to 95:5 in a gold lined pressure reaction vessel to form a reaction mixture; 2) heating the mixture at a temperature from about 625 k to about 875 k at a pressure from about 40,000 psi (267 MPa) to about 70,000 psi (467 MPa).
11. A process for converting a mixture of methane and propane to higher molecular weight hydrocarbons said process comprising heating in the absence of catalyst the methane/propane mixture in a volume ration of from 5:95 to 95:5 at a temperature of from about 625 k to about 875 k at a pressure of from about 30,000 psi (200 MPa) to about 70,000 psi (467 MPa) to produce one or more higher hydrocarbons having up to 12 carbon atoms selected from the group consisting of branched or straight chain alkanes, branched or straight chain unsaturated aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons.
2. The process of
3. The process of
6. The process of
a) methane, ethane, n-butane, isobutane, pentane, isopentane, neopentane, n-hexane, 2-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, n-heptane, 2-methylhexane, 2-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2,3-trimethylbutane, 2,3,4-trimethylpentane, heptane, 2-methylheptane, octane, nonane, decane, 2,2-dimethylheane, 2,7-dimethyloctane and their mono and diunsaturated hydrocarbons comprsing 1-propane, 1-butene, 2-methyl-1-propene, 1-pentene, 2-pentene(2), 2-pentene, (E), 2-methyl-1-butene; 2-methyl-1-butnee, 2-methyl-2-butene, 1-hexene, 2-methyl-1-pentene, 3-methyl-2-pentene (Z), 2,3-dimethyl-2-butene, 3-hexene (Z), 2,4-dimethyl-1-pentene, 4,5-dimethyl-1-hexene, 3,3-dimethyl-1-hexene, 2,8-dimethyl-1,8-nonadiene, 5-methyl-1-heptene; b) cyclopentene, 1,3-dimethyltranscyclopentane, 1,2-dimethyltranscyclopentane, 1,1,2-trimethylcyclopropane, cyclohexane, methylcyclohexane, benzene, and methylbenzene.
8. The process of
10. The process of
14. The process of
|
|||||||||||||||||||||||||||||||||||||
This application is a continuation of application Ser. No. 07/380,190, filed July 14, 1989, now abandoned.
This invention relates to the isomerization of lower alkanes even in the absence of catalyst to give a variety of hydrocarbons containing up to twelve carbon atoms.
Methane is a very stable molecule with a C--H bond energy of 105 kcal/mole relatively inert to chemical reaction at temperatures where thermal dissociation is negligible. In the absence of a catalyst measurable dissociation of methane does not occur below 525°C (Egloff, Reactions of Pure Hydrocarbons, pp 38-39, 1937). Methane reaction with saturated hydrocarbons such as alkanes and cycloalkanes has not been detected. Unsaturates like acetylenes and lower olefins, however, react with methane at ambient temperatures, but under exceptional catalytic conditions --a Ziegler-Natta system for acetylene insertion into methane (Grigoryan et al, 1981) or a strong acid system, TaF5 --HF for alkylation by olefins (Siskin and Mayer, 1978). Aromatics, the major unsaturated hydrocarbon constituents of petroleum, do not react with methane at ordinary temperatures and pressures. The alkylation of benzene with methane, however, could occur either under conditions such as high-frequency electrodeless gaseous discharge (Prilezhaeva and Noether, 1937) or in the presence of catalysts, such as NiO--Al2 O3 (Rieche and Seeboth, 1963), or Ni-Al2 O3 (Rieche et al., 1964) or a strong acid system, for example, anhydrous fluoroantimonic acid (Olah et al., 1975). The addition of methane to benzene under non-pyrolytic as well as pyrolytic conditions (MacKenzie and Growcock, 1977) has resulted in the formation of toluene in varying yields. Alkylation of phenol with methane over solid acids and bases such as SiO2 --Al2 O3 , MgO--Al2 O3, SiO2 --Al2 O3 and MgO at temperatures where significant methane pyrolysis occurs (above 650° C.) produced mixtures of cresols and xylenols in varying yields (Nishizaki and Tanabe, 1973). Recently Dabrowski (1980) has reported selective orthoalkylation of phenols by methane catalyzed by NiO supported on MgO, to 2,6-xylenol. In all these cases the addition of methane onto the aromatic ring resulted in the incorporation of "one carbon unit", or methylation of the ring.
In order to assess the possible role of methane in petroleum formation, Gold et al (Geochimica et Cosmochimica Acta Vol. 50, 2411-2418 (1986)) studied the reaction of methane with liquid aromatic hydrocarbons at 15,000 psi (100 MPa) and 150-250°C in the presence of montmorillonite clay catalyst using 14 C labeled methane to trace reaction products. Reaction of methane with benzene gave predominantly C2 addition while only very small amounts of C1 addition were detected.
Because of the availability of lower alkanes, there is a need to synthesize higher hydrocarbon from these resources. Prior art references have suggested that hydrocarbons subjected to high pressures and temperatures greater than 300°C (573 K)would equilibrate to mixtures of methane and carbon (soot) The present invention relates to the conversion of C1 -C3 hydrocarbons or mixtures thereof in the absence of catalyst to give higher hydrocarbons.
FIG. 1 represents a schematic diagram of the system used for hydrocarbon synthesis under high pressure and temperature.
FIG. 2 represents a cross-sectional side view of the high pressure vessel with gold coated reaction chamber.
FIG. 3 represents a schematic diagram of the sampling system used.
FIGS. 4 thru 11 show distribution of synthesized higher hydrocarbons versus time by reacting propane at 723 K and 60,000 psi (400 MPa).
One object of the present invention relates to a process for converting a feedstock comprising one or more C1 -C3 hydrocarbons to a product hydrocarbons having up to 12 carbon atoms which comprises heating even in the absence of catalyst one or more C1 -C3 alkane hydrocarbons at a temperature from about 673 K to about 723 K, preferably about 673 K at a pressure from about 40,000 psi (267 MPa)to about 70,000 psi (467 MPa), preferably about 60,000 psi (400 MPa); wherein said product comprises at least one of the following: branched or straight chain alkane hydrocarbons; branched or straight chain unsaturated aliphatic hydrocarbons; cycloalkanes and aromatic hydrocarbons.
Another object relates to the conversion of propane or methane to higher hydrocarbons.
A yet further object relates to the conversion of mixtures of methane and propane to higher hydrocarbons.
The invention relates to the conversion of lower alkane hydrocarbons to higher product hydrocarbons by reacting one or more C1 -C3 hydrocarbons in the absence of catalyst at temperature of from about 673 K to about 873 K, preferably about 673 K and pressures of from about 40,000 psi (267 MPa) to about 70,000 psi (467 MPa), preferably about 60,000 psi (400 MPa) for a time sufficient to produce the desired hydrocarbon product or mixtures thereof including those products shown in the best mode examples.
By hydrocarbon products or product hydrocarbons is meant one or more hydrocarbons containing up to about 12 carbon atoms or their unsaturated counterparts obtained by reacting C1 -C3 hydrocarbons or mixtures thereof under the temperature and pressure conditions set forth herein. While it is not certain how the variety of products are formed, it is believed that the higher hydrocarbons result by addition of C1 and C2 fragments generated during the course of the reaction.
A second aspect of the invention relates to the non-catalyzed addition of methane to paraffin hydrocarbons to yield hydrocarbon products resulting from both C1 and C2 carbon additions.
As shown in the best mode examples, mixtures of methane and propane react at pressure and temperatures up to about 773 K primarily by alkylation of the propane at the secondary carbon.
As shown in Table 1, 80%/20% methane/propane mixtures at 700 K, 400 MPa and 95 minute reaction time show a decrease in methane content, increase in propane content and the production of isopentane, butane, isobutane and pentane. As shown in Table 2 of Example 2, a 50%/50% methane/propane mixture at 723 K and (400 MPa) pressure appears to produce small quantities of benzene and hexane at 132 hours and 183 hours reaction time.
By heating methane alone for two weeks at a temperature of 673 K and 32000 psi (213 MPa), no rearrangement products were detected. It would appear that methane is favored under these conditions.
By controlling the temperature and pressure and without the addition of catalyst, it is possible to convert one or more lower alkanes (C1 -C3) to a variety of hydrocarbons including alkanes, alkenes, cycloalkanes, cycloalkenes and aromatic hydrocarbons. Examples of alkanes which can be produced include, methane, ethane, propane, butane, isobutane (secondary butane), pentane, isopentane, neopentane, hexane, isohexane, and the like.
As shown in Example 5, the reaction of pure propane in the gold lined reactor at 723 K and 60000 psi (400 MPa) produce an entire sequence of products ranging from propane to cyclopentane and cyclohexane, and aromatics such as benzene and methylbenzene (see Table 4). The various products and their appearance and disappearance as the reaction proceeds over a thirty hour period are shown in a series of product plots versus time, FIGS. 4 through 11. FIG. 4 shows the time relationship of methane, ethane and propane. FIG. 5 shows the time plots for butane, pentane, hexane, heptane and octane. FIG. 6 shows that 2-methyl propane increases in amounts greater than 2-methyl butane and 2-methyl pentane. FIG. 7 shows the production of unsaturated products containing up to 5 carbon atoms, namely 1-propene; 1-butene; 2-pentene; and 1-pentene in that order. FIG. 8 shows the production of branched species, namely 2,2-dimethyl butane, 2,3-dimethyl butane, 2,2-dimethyl propane, and 2-methyl 1-propene. FIG. 9 shows the production of higher branched species, namely 4-methyl 1-hexane, 2,4- dimethyl pentane, 2-methyl hexane, and 3-methyl hexane.
FIG. 10 shows trace species of cycloalkanes, C7 alkanes and aromatics, namely heptane, 2-methyl 2-butane, 2,2-dimethyl pentane, benzene, and 1,3-dimethyl transcyclopentane.
FIG. 11 shows production of other trace species, namely, 2,2,3-trimethyl butane, methyl cyclohexane, 1,2-dimethyl transcyclopentane, 2-methyl-l-butane, and cyclohexane.
The alkylation apparatus comprises a vessel of Inconel 718, preferably internally coated with a layer of metal such as gold to prevent hydrogen permeation. The apparatus is equipped with ancillary pressure generation equipment capable of the full range of pressures of interest, namely pressures up to 150,000 psi (1.0 GPa) and preferably in the range of from about 15,000 (100 MPa) to about 100,000 psi (667 MPa). The apparatus is shown in FIGS. 1 and 2.
FIG. 1 represents a schematic diagram of the Inconel 718 reactor system for hydrocarbon synthesis under high pressure and temperature. The reactor vessel (2), surrounded by oven atmosphere chamber (4) having controlled atmosphere input (6) and exhaust port (8), is enclosed within oven (10) having a heater mechanism (14) controlled by oven controller (16). Controlled atmosphere (N2, CO2, etc.) inlet (6) is provided with a preheater (18). Chamber 4 surrounding reaction vessel (2) is ducted to exit port (8) using exhaust fan (12). Reactor inlet capillary (20), used for charging the reactor, also contains hypodermic needle sampling lines connected to sample ports (26) and (28). Reactant pressure is provided by compressor (30) or screw driven pump (35), augmented by pressure intensifier (34), through inlet tube (20) to the reactor vessel (2). Pressure is measured wing manganin pressure gauge (36).
FIG. 2 represents a cross section side view of the Inconel 718 reactor system (2) comprising a 3" long cylindrical chamber (36) internally coated or plated with a metal such as silver or gold; said cylinder being the cavity derived from Inconel block (38), closed at the top by a seal consisting of hollow mushroom stem (44) with internal gold plating (42) allowing for loading methane and hydrocarbon starting materials, said stem positioned and held in place by drive nut (46) and sealed by Inconel 718 spacers (48) and surrounding metal (Ag) ring seals (50) assembly, said seal tightened initially using mild steel spacer (52). Chamber (36) is sealed at the bottom by dead end plug (56) with Au wire rings (58), silver seal (60) and brass anti-extrusion rings (70) atop Inconel 718 drive nut (62). The seal at dead end plug (56) is tightened initially by mild steel nut (64). Weep holes (66) access the regions just outside the seals and allow gas to exit through the exhaust port (68) to detect chamber integrity.
An electric oven controls the temperature of the vessel within 5 K and serves as part of the safety shielding. Samples were taken from either the top or the bottom of the vessel volume using hypodermic needle tubing which enters the vessel through the vessel fill line (20). Samples were analyzed on a gas chromatograph equipped with a mass spectrometer detector and/or by a gas chromatograph alone. Detection limits are on the order of parts per million.
The pressure reactor (2) is a thick-walled monoblock autofrettaged vessel of Inconel 718, with an internal volume of approximately 10 em3, gold plated internal surfaces, a wall ratio of 8:1, and a calculated burst pressure of better than 1.5 GPa at 1000 K. The vessel resides in a steel jacketed electrical oven (10) with on/off temperature control. The temperature is stable to within 5 K under normal operation. The oven is flushed with an inert gas to minimize the possibility of combustion should a leak develop at high temperature. Although the pressure generation equipment is capable of developing pressures up to 2 GPa, operation with pressures above 1 GPa is not recommended. Hypodermic needle tubing enters the vessel through the inner bore of the connecting tubing (20) and allows for sampling of the vessel contents during operation. The samples may be drawn from either the top or the bottom of the vessel, allowing detection of phase instability. Due to the extremely small bore of the hypodermic needle tubing, the samples are easily throttled from the vessel pressure into an evacuated chamber, to attain a final pressure of 15 psig (200 kPa). These samples may then be drawn into syringes at (26) or (28) and injected into a gas chromatograph for analysis. All portions of the apparatus that are exposed to the high pressure fluid reside behind shielding of 1/8inch steel clad with 3/8inch plywood. The oven effluent (due to the inert purge) is ducted (8) to the outdoors. The apparatus is operated entirely from outside the safety shielding.
Temperature measurement is accomplished using a thermocouple in physical contact with the vessel. The pressure is measured using a manganin wire coil (36) external to the oven. The temperature may also be measured at the heated purge gas inlet (6) on the oven to prevent development of a thermal gradient within the oven. Temperature control is accomplished using a platinum resistance temperature device (RTD) as one leg of a Wheatstone bridge. The bridge output is fed to a comparator, which in turn operates a relay through which the oven heaters are powered. Thus, the control is of the simple on/off type.
The sampling method consists of drawing samples from within the vessel, either at the top or the bottom portions of the vessel interior, through hypodermic needle tubing. The tubing is of 304 stainless steel, 0.009 inches in O.D. with a 0.004 inch thick wall, is gold plated on the outer diameter, and accesses the vessel through the interior of the 1/8inch capillary tubing that connects the vessel to the pressure generation and measurement equipment. After leaving the vessel, the two lines pass through the 1/8inch cross fitting and diverge at the beryllium-copper Y fitting. Each then proceeds to its associated high pressure sampling valve.
The sampling procedure is as follows: a syringe, fitted at the needle with a gas tight valve, is connected to the system through one of the septa and the needle, syringe (with the plunger fully depressed and the valve open), sampling chamber, volume behind the septum and the associated relief valve, tubing, and sampling valve interior are evacuated (see FIG. 3). The vacuum system is then isolated and the sampling valve is cracked open until the pressure in the sampling system (as measured by the bourdon tube gauge) reaches ≈15 psig. and the relief valve cracks open. The high pressure valve is then shut, and the plunger of the syringe is withdrawn to the desired volume. The gas tight valve on the syringe is closed, the syringe is withdrawn from the septum, and the remaining sample is dumped to the vacuum system. The syringe is then transported to the gas chromatograph or the GC/MS. Two samples were taken when the oven reached the desired temperature (i.e. 727 K). These were marked as taken at t- 0 minutes at temperature. Samples were taken at intervals of one hour, extending the time between samples as the experiment progressed.
Samples are analyzed using either a gas chromatograph (Hewlett-Packard model number 5890A) with an Al2 O3 KCl PLOT (Porous Layer Open Tubular) capillary column (Chrompack International catalogue number 7517) a thermal conductivity detector (TCD), and a Hewlett-Packard integrator (model number 3392A); or a Hewlett-Packard GC/MS (Gas Chromatograph/Mass Spectrometer, GC model number 5880A and mass selective detector (MSD), model number 5970B) equipped with a TCD, a crosslinked methyl silicone capillary column and a computer library of 38,791 mass spectra. The operating parameters for the GC were: split flow: 47.60 ml/s; total flow through detector: 11.32 ml/s; reference and column flow: 7.90 ml/s; column flow, alone: 3.87 ml/s; Tinjector and Tdetector : 150° C.; T column; 130°C, ramped to 200°C; column head pressure: 10 psi; sample size: 500 μl at atmospheric pressure; and carrier make up gas: He (99.9% pure). The GC/MS operating parameters were: Electron energy: 70 eV; scan range of 10-100 AMU; 10-300 AMU, and 10-550 AMU for respective time periods of 0-20 min; 20-35 min; and 35-45 min; sample size was 500 μl at atmospheric pressure using He carrier makeup gas; temperature of injector: 100°C temperature detector: 300°C temperature columns: -80°C, ramped to 200° C.
In addition to the experiments, calculations were made using a flexible computer program. NEWTRAPH, which minimizes the Gibbs free energy of the mixture at prescribed conditions of pressure, temperature, and H to C atomic ratio. The program can handle at least 20 species and up to 5 elements such as H, C, N, 0, and S. Any of four equations of state may be used to calculate the fugacity coefficient of each of the species.
These calculations show significant quantities of C2 and higher order hydrocarbons would result at high temperatures (to the full 1000 K), given high enough pressures. A stability boundary (in pressure-temperature space) is mapped out using this program, providing a crude guide as to which conditions will cause a system to undergo thermal decomposition to methane, hydrogen, and/or soot. The calculations of the chemical equilibrium of the experimental systems agree qualitatively with the experimental results.
The following examples represent experiments illustrative of the invention but should not be construed as limiting the invention thereto. Unless otherwise specified, the reactor as described herein was one having a gold plated interior surface; pressures are given in mega pascals; and temperatures in degrees Kelvin.
PAC Reaction of Propane/Methane Mixtures (20/80)Using the pressure vessel in the Detailed Description of the Invention, a mixture of 20 percent propane/80 percent methane reacted at 700 K and 60,000 (400 MPa) psi. The results are shown in Table 1. Samples were taken at 95 minutes and 165 minutes. Products were detected by Gas Chromatogram/Mass Spectra GS/MS and reported as detector area fractions. The formation of 2-methyl propane and 2-methyl butane (2-ethyl propane) was noted with the disappearance of trace impurities of ethane and ethylene.
| TABLE 1 |
| ______________________________________ |
| GC/MS Output (Numbers given are detector area fractions) |
| Starting Reagents: 20% Propane, 80% Methane, |
| T = 700K, P = 400 MPa |
| Species blank blank 0 min. 95 min. |
| 165 min. |
| ______________________________________ |
| methane .820000 .801000 .696000 |
| .573000 |
| .920000 |
| CO2 .000576 .000237 .001226 |
| ethane .002000 .001900 |
| propane .180000 .196000 .303000 |
| .421000 |
| .077700 |
| isobutane .000636 |
| .001520 |
| butane .000486 |
| isopentane .002790 |
| .003130 |
| pentane .000986 |
| ______________________________________ |
The procedure of Example 1 was repeated using 50 percent propane/50 percent methane at the temperature of 723 K and a pressure of 60,000 psi (400 MPa). Duplicate samples were taken at 36, 84, 132, 183 and 228 hours. Results by GC/MS (detector area fractions) are shown in Table 2. Despite heavy air contamination, the samples indicated the production of benzene.
| TABLE 2 |
| ______________________________________ |
| GC/MS Output from Experiment |
| (Numbers given are detector area fractions) |
| Starting Reagents: 50% Propane, 50% Methane, |
| T = 723K, P = 400 MPa. |
| ______________________________________ |
| Species blank blank 36 hrs 36 hrs |
| 84 hrs |
| 84 hrs |
| ______________________________________ |
| methane .516400 .582500 .7797 .940100 |
| CO2 |
| .000079 .000241 .036200 |
| .133300 .000945 |
| ethane .006631 .001243 |
| propane .479000 .410600 .848200 |
| .375100 |
| .021200 |
| .054600 |
| isobutane |
| .001630 .001651 |
| water .002357 .005098 .108900 |
| .491600 |
| .199200 |
| .003189 |
| butane .000351 |
| ______________________________________ |
| Species 132 hrs 132 hrs 183 hrs |
| 183 hrs |
| 228 hrs |
| ______________________________________ |
| methane .928800 .809986 .908400 |
| .894800 |
| .992000 |
| CO2 |
| .000143 .000229 .000568 |
| .000258 |
| .000931 |
| ethane .038960 .020000 .007376 |
| .011000 |
| propane .027100 .167700 .077700 |
| .085400 |
| .005833 |
| isobutane .000645 |
| water 004533 .000745 .006014 |
| .007622 |
| .001264 |
| benzene(?) |
| .000535 .008791 |
| hexane(?) .000850 |
| ______________________________________ |
| reagent meth- iso- |
| assays ane CO2 |
| propane |
| butane |
| water butane |
| ______________________________________ |
| C3 H8 blank |
| .00119 .99383 .00115 .00383 |
| CH4 blank |
| .983800 .001173 .015100 |
| ______________________________________ |
In two runs using methane at 673 K and 32,000 psi (213 MPa) for periods of 6 hours and for 2 weeks, no products other than starting methane were detected.
Using the Inconel 718 pressure vessel (having at the time an internal silver coating) shown in FIG. 2, methane (10 ml) was heated at a temperature of 673 K and a pressure of 32000 psi (213 MPa) for a period of 6 hours. No rearrangment or addition products were detected by gas chromatography/mass spectroscopy. Although the samples were tainted by air, this run demonstrated that no rearrangement would take place with a H/C ratio of 4:1 as separately predicted by equilibrium calculations. It was doubted that equilibrium had been reached at this temperature.
The reaction was repeated at 673 K and 32000 psi (213 MPa) for a period of 2 weeks. No rearrangement or addition products were detected. This run was approximately as air free as Example 1; the greater reaction time supports the conclusion that the equilibrium of a hydrocarbon system with an H/C ratio of 4:1 at 673 K and 32,000 psi (213 MPa) lies at methane. The run ended when the RTD used by the oven controller failed.
PAC Pure PropanePure Propane (source Matheson) was heated at 773 K and 60,000 psi (400 MPa). Samples taken at 100, 200 and 250 minutes were analyzed by gas chromatography. Results shown in Table 3 indicate methane increase with time of reaction and production of butane, 2-methyl butane and pentane with decrease in amounts of starting propane.
| TABLE 3 |
| ______________________________________ |
| GO Output (Numbers given are detector area fractions) |
| Starting Reagent: Pure Propane, T = 773K, P = 400 MPa |
| Species blank 0 min. 100 min. |
| 200 min. |
| 250 min. |
| ______________________________________ |
| methane, TOV |
| .00336 .01774 .16582 .50597 .80640 |
| methane, BOV |
| .00161 .10389 .95074 |
| ethane, TOV |
| trace .00873 .04207 .06483 .07050 |
| ethane, BOV |
| trace .08016 |
| propane, TOV |
| .98940 .96293 .77146 .41556 .12310 |
| propane, BOV |
| .99299 .77880 .03913 |
| butane, TOV |
| .00294 .00536 .01006 .00641 |
| butane, BOV |
| .00352 .01875 .00385 |
| 2-methyl .00384 .00924 .00648 |
| butane, TOV |
| 2-methyl .00188 .01718 |
| butane, BOV |
| pentane, TOV .00069 .00068 |
| pentane, BOV .00123 .00221 |
| ______________________________________ |
Propane was reacted at 723 K and a pressure of 60,000 psi (400 MPa). Samples taken at 1, 2, 3, 4, 5, 35, 9, 13, 18, 27 and 39 hours were analyzed by GS/MS. Results are shown in Table 4. Major components were reported as detector area fractions while trace products were given in part per million again, as detectors area fractions. For clarification of the production of various higher hydrocarbon species, the GS/MS data from Table 4 are selectively plotted with time in FIG. 4 (1-3 carbon species); FIG. 7 (normal alkenes); FIG. 8 (branched species); FIG. 9 (branched species); FIG. 10 (trace species including benzene, heptane and 1,3-dimethyl transcyclopentane; and FIG. 11 (trace species, cyclohexane, methylcyclohexane, 2,2,3-trimethylbutane etc.).
As soon in Table 4, one or more of the following hydrocarbon products result when propane is heated at 723 K and a pressure of 60,000 psi (400 MPa):
a) methane, ethane, n-butane, isobutane,pentane, isopentane, neopentane, n-hexane, 2-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, n-heptane, 2-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,2,3-trimethylbutane, 2,3,4-trimethylpentane, heptane, 2-methylheptane, octane, nonane, decane 2,3-dimethylhexane, 2,7-dimethyloctane and their mono and di-unsaturated hydrocarbons comprising 1-propene, 1-butene, 2-methyl-1-propene, 1-pentene, 2-pentene(2), 2-pentene (E), 2-methyl-1-butene; 2-methyl-1-butnee, 2-methyl-2-butene, 1-hexene, 2-methyl-1-pentene, 3-methyl-2-pentene (Z), 2,3-dimethyl-2-butene, 3-hexene (Z), 2,4-dimethyl-1-pentene, 4,5-dimethyl-1-hexene, 3,3-dimethyl-1-hexene, 2,8-dimethyl-1,8-nonadiene, 5-methyl-1-heptene;
b) cyclopentene, 1,3-dimethyltranscyclopentane, 1,2-dimethyltranscyclopentane, 1,1,2-trimethylcyclopropane, cyclophexane, methylcyclohexane, benzene, and methylbenzene.
| TABLE 4 |
| __________________________________________________________________________ |
| GC/MS Data |
| Starting Reagent: Pure Propane, T = 723K, P = 400 MPa |
| Species 240 min. |
| 321 min. |
| 540 min. |
| 780 min. |
| 1080 min. |
| 1620 m |
| __________________________________________________________________________ |
| methane .20670 |
| .10835 |
| .76617 |
| .30507 |
| .22801 |
| .26822 |
| carbon dioxide |
| 618 ppm |
| 327 ppm |
| 2799 ppm |
| 317 ppm |
| 527 ppm |
| 420 ppm |
| ethane .03137 |
| .10488 |
| .10790 |
| .16264 |
| .18483 |
| .21772 |
| 1-propene 262 ppm |
| 591 ppm |
| 57 ppm |
| 787 ppm 814 ppm |
| propane .73409 |
| .52581 |
| .16765 |
| .29843 |
| .31855 |
| .25583 |
| 2-methyl .01946 |
| .04176 |
| .01839 |
| .07113 |
| .08103 |
| .08602 |
| propane |
| 2-methyl 1030 ppm |
| 3603 ppm |
| 335 ppm |
| 2542 ppm |
| 119 ppm |
| 2095 ppm |
| 1-propane |
| butane .01270 |
| .03664 |
| .01028 |
| .05044 |
| .05335 |
| .05295 |
| 2,2-dimethyl 835 ppm |
| 336 ppm |
| 2276 ppm |
| 4148 ppm |
| 5062 ppm |
| propane |
| 1-butene 287 ppm 272 ppm |
| 277 ppm |
| 281 ppm |
| 3-methyl 170 ppm 110 ppm |
| 85 ppm |
| 96 ppm |
| 1-butene .03905 |
| .04363 |
| .01087 |
| .03714 |
| .03548 |
| .03359 |
| 2-methyl |
| butane |
| 1-pentene 121 ppm 98 ppm |
| 109 ppm |
| 102 ppm |
| 2-methyl 468 ppm 332 ppm |
| 332 ppm |
| 333 ppm |
| 1-butane |
| pentane .01165 |
| .02165 |
| 4246 ppm |
| .02045 |
| .02457 |
| .02511 |
| 2-pentene (Z) 378 ppm 247 ppm |
| 281 ppm |
| 265 ppm |
| 2-pentene (E) 2201 ppm 136 ppm |
| 154 ppm |
| 165 ppm |
| 2-methyl 528 ppm 162 ppm |
| 900 ppm |
| 839 ppm |
| 804 ppm |
| 2-butene |
| 2,2-dimethyl |
| 527 ppm |
| 2193 ppm |
| 398 ppm |
| 3323 ppm |
| 5722 ppm |
| 6142 ppm |
| butane |
| cyclopentene 18 ppm |
| 22 ppm |
| 4-methyl 133 ppm 38 ppm |
| 50 ppm |
| 47 ppm |
| 1-pentene |
| 2,3-dimethyl |
| 3631 ppm |
| 8388 ppm |
| 687 ppm |
| 3915 ppm |
| 5247 ppm |
| 4489 ppm |
| butane |
| 2-methyl .01706 |
| .03162 |
| 3592 ppm |
| .01562 |
| .01822 |
| .01535 |
| pentane |
| 4-methyl 431 ppm |
| 2040 ppm |
| 1743 ppm |
| 2138 ppm |
| 3986 ppm |
| 3621 ppm |
| 1-hexene |
| 2-methyl 244 ppm 110 ppm |
| 132 ppm |
| 101 ppm |
| 1-pentene |
| hexane 8376 ppm |
| .01944 |
| 1486 ppm |
| 7905 ppm |
| .01108 |
| 7230 ppm |
| 3-methyl 45 ppm |
| 261 ppm |
| 172 ppm |
| 2-pentene (Z) |
| 2,3-dimethyl 745 ppm 133 ppm |
| 81 ppm |
| 40 ppm |
| 2-butene 145 ppm 53 ppm |
| 56 ppm |
| 18 ppm |
| 3-hexene (Z) |
| 1,1,2-trimethyl |
| 170 ppm 47 ppm |
| 77 ppm |
| 35 ppm |
| cyclopropane |
| 2,2-dimethyl |
| 341 ppm |
| 1052 ppm |
| 24 ppm |
| 621 ppm |
| 1415 ppm |
| 964 ppm |
| pentane |
| 2,4-dimethyl |
| 6402 ppm |
| .01279 |
| 721 ppm |
| 4215 ppm |
| 6190 ppm |
| 3878 ppm |
| pentane |
| 2,2,3-trimethyl |
| 391 ppm |
| 953 ppm 329 ppm |
| 431 ppm |
| 234 ppm |
| butane |
| 2,4-dimethyl 144 ppm 40 ppm |
| 25 ppm |
| 1-pentene |
| benzene 299 ppm 265 ppm |
| 777 ppm |
| 873 ppm |
| 4,5-dimethyl 374 ppm 224 ppm |
| 328 ppm |
| 198 ppm |
| 1-hexene |
| cyclohexane 159 ppm |
| 311 ppm |
| 218 ppm |
| 2-methyl 8857 ppm |
| .01851 |
| 811 ppm |
| 4507 ppm |
| 6377 ppm |
| 3201 ppm |
| hexane |
| 3-methyl 703 ppm |
| 2382 ppm |
| 20 ppm |
| 1081 ppm |
| 2026 ppm |
| 1162 ppm |
| hexane |
| 1,3-dimethyl 607 ppm 826 ppm |
| 1100 ppm |
| 646 ppm |
| transcyclopentane |
| 1,2-dimethyl 707 ppm 410 ppm |
| 212 ppm |
| transcyclopentane |
| heptane 494 ppm |
| 2290 ppm 565 ppm |
| 1086 ppm |
| 479 ppm |
| 3,3-dimethyl 16 ppm 8 ppm |
| 1-hexane |
| 2,8-dimethyl 19 ppm |
| 1,8-nonadiene |
| 2,2-dimethyl 35 ppm 19 ppm |
| 86 ppm |
| 47 ppm |
| hexane |
| methyl cyclohexane |
| 682 ppm 261 ppm |
| 597 ppm |
| 287 ppm |
| 2,7-dimethyl octane |
| 495 ppm 72 ppm |
| 206 ppm |
| 85 ppm |
| 2-undecene (Z) 401 ppm 76 ppm |
| 316 ppm |
| 138 ppm |
| 5-methyl 171 ppm 23 ppm |
| 102 ppm |
| 34 ppm |
| 1-heptene |
| 4,5-dimethyl 92 ppm 28 ppm |
| 1-hexene |
| methyl benzene 311 ppm 14 ppm |
| 252 ppm |
| 136 ppm |
| 2-methyl heptane |
| 483 ppm 15 ppm |
| 163 ppm |
| 49 ppm |
| octane 270 ppm 100 ppm |
| 31 ppm |
| nonane(?) 38 ppm 32 ppm |
| 2-methyl 79 ppm |
| pentanal |
| decane(?) 7 ppm |
| __________________________________________________________________________ |
Zemanian, Thomas S., Streett, William B., Gold, Thomas, Zollweg, John A.
| Patent | Priority | Assignee | Title |
| 11624271, | Nov 04 2019 | Method for enhancing oil recovery from groups of wells | |
| 5595709, | Sep 01 1992 | Chromatofast | Instrument for measuring non-methane organic gases in gas samples |
| 6130260, | Nov 25 1998 | The Texas A&M University Systems | Method for converting natural gas to liquid hydrocarbons |
| 6602920, | Nov 25 1998 | The Texas A&M University System | Method for converting natural gas to liquid hydrocarbons |
| 7119240, | Nov 25 1998 | The Texas A&M University System | Method for converting natural gas to olefins |
| 7955571, | May 27 2008 | China Academy of Sciences Guangzhou Earth Chemistry Research Institute | Intermittently opened cracking crude oil apparatus |
| 8062503, | Mar 01 2007 | IVANHOE HTL PETROLEUM LTD | Products produced from rapid thermal processing of heavy hydrocarbon feedstocks |
| 9005428, | Sep 18 2000 | IVANHOE HTL PETROLEUM LTD | Products produced from rapid thermal processing of heavy hydrocarbon feedstocks |
| 9650575, | Mar 13 2015 | MechCracker Corporation | Cavitation hydrocarbon refining |
| 9707532, | Mar 04 2013 | IVANHOE HTL PETROLEUM LTD | HTL reactor geometry |
| Patent | Priority | Assignee | Title |
| 2373303, | |||
| 3209046, | |||
| 3251897, | |||
| 3396206, | |||
| 4524230, | Jun 08 1984 | UOP, DES PLAINES, IL, A NY GENERAL PARTNERSHIP | Preparation of alkylaromatic compounds |
| 4769507, | Mar 30 1987 | National Distillers and Chemical Corporation | Process for making higher hydrocarbons from methane |
| 4780449, | Jun 14 1985 | W. R. Grace & Co.-Conn. | Catalyst for the conversion of methane |
| 4822938, | May 03 1988 | MOBIL OIL CORPORATION, A CORP OF NY | Processes for converting methane to higher molecular weight hydrocarbons via sulfur-containing intermediates |
| 4822941, | Feb 12 1987 | Mobil Oil Corporation | Conversion of aliphatics to aromatics over a zeolite catalyst |
| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| May 03 1991 | Cornell Research Foundation, Inc. | (assignment on the face of the patent) | / |
| Date | Maintenance Fee Events |
| Jul 25 1995 | REM: Maintenance Fee Reminder Mailed. |
| Dec 17 1995 | EXP: Patent Expired for Failure to Pay Maintenance Fees. |
| Date | Maintenance Schedule |
| Dec 17 1994 | 4 years fee payment window open |
| Jun 17 1995 | 6 months grace period start (w surcharge) |
| Dec 17 1995 | patent expiry (for year 4) |
| Dec 17 1997 | 2 years to revive unintentionally abandoned end. (for year 4) |
| Dec 17 1998 | 8 years fee payment window open |
| Jun 17 1999 | 6 months grace period start (w surcharge) |
| Dec 17 1999 | patent expiry (for year 8) |
| Dec 17 2001 | 2 years to revive unintentionally abandoned end. (for year 8) |
| Dec 17 2002 | 12 years fee payment window open |
| Jun 17 2003 | 6 months grace period start (w surcharge) |
| Dec 17 2003 | patent expiry (for year 12) |
| Dec 17 2005 | 2 years to revive unintentionally abandoned end. (for year 12) |